In this study, we demonstrate the use of elemental precursors (Cu,Sb,S) to synthesize tetrahedrite Cu₁₂Sb₄S₁₃ using an industrial eccentric vibratory mill. Mechanochemical synthesis of tetrahedrite leads to the formation of covellite (CuS), skinnerite (Cu₃SbS₃) or famatinite (Cu₃SbS₄) in dependence on milling time. However, the composite product can be modified in favour of prevailing tetrahedrite when Spark Plasma Sintering (SPS) treatment is applied after milling. The as-synthesized and sintered products are composed of polydisperse nanosized particles with dimensions up to 250 nm. The thermoelectric measurements reveal a maximum value of figure-of-merit ZT = 0.67 @ 700 K, as a consequence of a relatively high power factor (1.07 mW m⁻¹ K⁻²) and a low thermal conductivity (1.12 W m⁻¹ K⁻¹). The obtained zT values of products prepared in an industrial mill are comparable to the ones reported for compounds synthesized using laboratory mills. The synthesis of ternary and quaternary sulphides by a scalable and industrializable milling process represents a prospective route for mass production of thermoelectric materials.

在这项研究中，我们证明了使用元素偏析物（Cu，Sb，S）使用工业偏心振动磨来合成四面体Cu ₁₂ Sb ₄ S ₁₃。四面体的机械化学合成导致依赖于研磨时间而形成钴铝石（CuS），蒙脱石（Cu ₃ SbS ₃）或辉铁矿（Cu ₃ SbS ₄）。但是，在铣削后进行火花等离子烧结（SPS）处理时，可以对复合产品进行改性，使其有利于占优势的四面体。合成和烧结后的产品由尺寸最大为250 nm的多分散纳米颗粒组成。热电测量显示品质因数的最大值由于较高的功率因数（1.07 mW m ^-1  K ^-2）和较低的热导率（1.12 W m ^-1  K ^-1），ZT = 0.67 @ 700K 。在工业工厂中制备的产品获得的zT值与使用实验室工厂合成的化合物所报告的zT值相当。通过可扩展和可工业化的研磨工艺合成三元和四元硫化物代表了热电材料大规模生产的一条前景之路。